Hair fixative film

ABSTRACT

The present invention relates to a hair fixative film, which contains a natural and/or synthetic polymer as the main component and a method of applying said film to hair. Such film is useful in maintaining a desired look and style of hair. Furthermore, the film is beneficial because it enables the combination of ingredients that are incompatible in other application forms.

BACKGROUND OF THE INVENTION

The present invention relates to a hair fixative film composition, andmethods of fixing and maintaining the hair in a given style by applyingsaid hair fixative film composition to the hair shafts.

A significant portion of the globe uses some sort of hair stylingproduct as part of a grooming routine. These styling products come in avariety of forms. These forms include non-aerosol and aerosol hairsprays, aerosol and non-aerosol mousses, gels, glazes, styling waters,spray gels, spray mousses, waxes, pastes, pomades, and ringing gels,among others. The overall market for these hair styling productscontinues to grow even though some specific categories have been flat ordeclining in recent years. There are many reasons for the market declineof some application types, but one reason is that each application hassome inherent limitations. These limitations can create performance andaesthetic weaknesses.

Ingredient incompatibility is one such limitation. For instance,incompatibilities between traditional gel thickening polymers andtraditional high performance styling polymers lead to less than idealproduct properties. These traditional high performance polymers providesuperior humidity resistance and setting power to common polymerscompatible in gels, but the combination with popular thickeners such ascarbomer, a cross-linked polyacrylate, results in hazy gels with poorrheology.

Additional application type limitations include the inability to includepolymers with poor solution stability, limits on polymer use levels,product bulkiness, and inconvenience of use. Therefore, there exists aneed for new application methods that deliver excellent hair fixativeproperties, have no negative ecological perceptions, provide formulationversatility, and are fun and convenient to use.

Recently, a new composition for delivering hair fixative polymers from astarch film has been disclosed in U.S. patent application 2003/0099692.Surprisingly, it has now been found that with proper formulationtraditional high performance hair fixative polymers can be formed intoacceptable films, which can be used as hair fixative films, without theaddition of starch or any other film forming polymer as the deliveryvehicle. It has also surprisingly been found that films containing hairfixative polymers can also be created containing starch and largeamounts of plasticizer. Such films may provide such benefits asexcellent high humidity curl retention, film toughness, gloss,stiffness, combing ease, static properties, spring, and webbing whenapplied to hair. In addition, such films may be more efficient as thehair fixative polymer is less diluted by the addition of othernon-functional ingredients.

SUMMARY OF THE INVENTION

The present invention relates to hair fixative film compositions,wherein such films function as hair fixatives when dissolved in polarsolvent and applied to the hair and/or are distributed through wet hair,and a method of fixing the hair by applying said hair fixative filmcompositions to the hair shafts. Another aspect of the invention relatesto the addition of hair fixative films to existing products to achieveincreased performance or add other additional properties to theproducts.

“Hair fixative film”, as used herein, means a film which is eithersupported on a backing or unsupported, dissolves in polar solvent atroom temperature, is applied and distributed through the hair by aconsumer, and will hold the hair in a desired conformation afterapplication. The hair fixative films may be single or multi-layered,embossed, textured and/or formed into different shapes.

“Dissolves in polar solvent” means that when the film is added to polarsolvent, or polar solvent is added to the film, that the film breaksapart or combines with the polar solvent to form a solution ordispersion so as to enable the spread of the composition through hair.The wettability or dissolution rates may be modified by one skilled inthe art to target a specific delivery profile.

“Hair fixative polymer”, as used herein, means any film forming polymerthat, when dissolved or dispersed and spread through hair, will fix thehair shafts in a given conformation and comprise natural and/orsynthetic polymers and may be either anionic, cationic, nonionic,amphoteric, or betaine polymers and used either alone or in combinationwith other natural and/or synthetic polymers.

“Synthetic” as used herein means not derived in any part from a plant,animal or bacteria.

“Natural”, as used herein, means derived or partially derived from aplant, animal or bacteria.

“Plasticizer”, as used herein, means any material that will contributeto making a film composition less brittle and more flexible.

“Base”, as used herein, means neutralizing agent and includes materialsthat will neutralize the free acid groups of a polymer.

“Dry”, as used herein, means substantially free of water and othersolvent, but does not mean the absence of water or solvent.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to hair fixative film compositionscomprising at least one hair fixative polymer, wherein such filmsfunction as hair fixatives when dissolved in polar solvent and appliedto the hair or distributed directly through wet hair. Another aspect ofthe invention is a method of fixing the hair by applying said hairfixative films to hair shafts. Potential benefits of the invention mayinclude the ability to combine ingredients incompatible in otherapplications, the ability to use high performance hair fixative polymersin non-spray applications, ecological friendliness, the ability to usehigh fixative polymer dosages, convenience of use, and small packagingsizes.

The film composition comprises at least one hair fixative polymer andmay be selected from the group consisting of a synthetic polymer, anatural polymer, or a mixture thereof.

The hair fixative polymer will be present in the hair fixative film inan amount great enough to effectively fix the hair after application ofthe film to hair. In one embodiment, the hair fixative polymer ispresent in an amount from about 50 percent to about 100 percent basedupon the weight of the hair fixative film. In another embodiment, thehair fixative polymer is present in an amount from about 60 percent toabout 95 percent based upon the weight of the hair fixative film. Inanother embodiment, the hair fixative polymer is present in an amountfrom about 70 percent to about 90 percent based upon the weight of thehair fixative film. In another embodiment, the hair fixative polymer ispresent in an amount from about 75 to about 90 percent based upon theweight of the hair fixative film.

The following are examples of synthetic hair fixative polymers suitablefor use in the present invention but in no way is meant to be limiting:from National Starch and Chemical Company, AMPHOMER and AMPHOMER LV-71polymers (octylacrylamide/acrylates/butylaminoethyl methacrylatecopolymer), AMPHOMER HC polymer (acrylates/octylacrylamide copolymer)BALANCE 0/55 and BALANCE CR polymers (acrylates copolymer), BALANCE 47polymer (octylacrylamide/butylaminoethyl methacrylate copolymer), RESYN28-2930 polymer (VA/crotonates/vinyl neodecanoate copolymer), RESYN28-1310 polymer (VA/Crotonates copolymer), FLEXAN polymers (sodiumpolystyrene sulfonate), DynamX polymer (polyurethane-14 (and)AMP-Acrylates copolymer), RESYN XP polymer (acrylates/octylacrylamidecopolymer), STRUCTURE 2001 (acrylates/steareth-20 itaconate copolymer)and STRUCTURE 3001 (acrylates/ceteth-20 itaconate copolymer); from ISP,OMNIREZ-2000 (PVM/MA half ethyl ester copolymer), GANEX P-904 (butylatedPVP), GANEX V-216 (PVP/hexadecene copolymer) GANEX V-220 (PVP/eicosenecopolymer), GANEX WP-660 (tricontanyl PVP), GANTREZ A425 (butyl ester ofPVM/MA copolymer), GANTREZ AN-119 PVM/MA copolymer, GANTREZ ES 225(ethyl ester of PVM/MA copolymer), GANTREZ ES425 (butyl ester of PVM/MAcopolymer), GAFFIX VC-713 (vinyl caprolactam/PVP/dimethylaminoethylmethacrylate copolymer), GAFQUAT 755 (polyquaternium-11), GAFQUAT HS-100(polyquaternium-28) AQUAFLEX XL-30 (Polyimide-1), AQUAFLEX SF-40(PVP/Vinylcaprolactam/DMAPA Acrylates Copolymer), AQUAFLEX FX-64(Isobutylene/Ethylmaleimide/Hydroxyethylmaleimide Copolymer), ALLIANZLT-120 (Acrylates/C1-2 Succinates/Hydroxyacrylates Copolymer), STYLEZECC-10 (PVP/DMAPA Acrylates Copolymer), STYLEZE 2000 (VP/Acrylates/LaurylMethacrylate Copolymer), STYLEZE W-20 (Polyquaternium-55), CopolymerSeries (PVP/Dimethylaminoethylmethacrylate Copolymer), ADVANTAGE S andADVANTAGE LCA (VinylcaprolactamNP/Dimethylaminoethyl MethacrylateCopolymer), ADVANTAGE PLUS (VA/Butyl Maleate/Isobornyl AcrylateCopolymer); from BASF, ULTRAHOLD STRONG (acrylic acid/ethylacrylate/t-butyl acrylamide), LUVIMER 100P (t-butyl acrylate/ethylacrylate/methacrylic acid), LUVIMER 36D (ethyl acrylate/t-butylacrylate/methacrylic acid), LUVIQUAT HM-552 (polyquaternium-16),LUVIQUAT HOLD (polyquaternium-16), LUVISKOL K30 (PVP) LUVISKOL K90(PVP), LUVISKOL VA 64 (PVPNA copolymer) LUVISKOL VA73W (PVPNAcopolymer), LUVISKOL VA, LUVISET PUR (Polyurethane-1), LUVISET Clear(VP/MethacrylamideNinyl Imidazole Copolymer), LUVIFLEX SOFT (AcrylatesCopolymer), ULTRAHOLD 8 (Acrylates/Acrylamide Copolymer), LUVISKOL Plus(Polyvinylcaprolactam), LUVIFLEX Silk (PEG/PPG-25/25Dimethicone/Acrylates Copolymer); from Amerchol, AMERHOLD DR-25 (acrylicacid/methacrylic acid/acrylates/methacrylates); from Rohm&Haas, ACUDYNE258 (acrylic acid/methacrylic acid/acrylates/methacrylates/hydroxy esteracrylates; from Mitsubishi and distributed by Clariant, DIAFORMER Z-301,DIAFORMER Z-SM, and DIAFORMER Z-400 (methacryloyl ethylbetaine/acrylates copolymer), ACUDYNE 180 (Acrylates/HydroxyestersAcrylates Copolymer), ACUDYNE SCP(Ethylenecarboxyamide/AMPSA/Methacrylates Copolymer), and the ACCULYNrheological modifiers; from ONDEO Nalco, FIXOMER A-30 and FIXOMER N-28(INCI names: methacrylic acid/sodium acrylamidomethyl propane sulfonatecopolymer); from Noveon, FIXATE G-100 (AMP-Acrylates/Allyl MethacrylateCopolymer), FIXATE PLUS (Polyacrylates-X), CARBOPOL Ultrez 10(Carbomer), CARBOPOL Ultrez 20 (Acrylates/C10-30 Alkyl AcrylatesCopolymer), AVALURE AC series (Acrylates Copolymer), AVALURE UR series(Polyurethane-2, Polyurethane-4, PPG-17/IPDI/DMPA Copolymer);polyethylene glycol; water-soluble acrylics; water-soluble polyesters;polyacrylamides; polyamines; polyquaternary amines; styrene maleicanhydride (SMA) resin; polyethylene amine; and other conventionalpolymer that is polar solvent soluble or that can be made solublethrough neutralization with the appropriate base.

Natural fixative polymers suitable for use in the present inventioninclude any single starch or combination of starches derived from anative source. A native starch as used herein, is one as it is found innature. Also suitable are starches derived from a plant obtained bystandard breeding techniques including crossbreeding, translocation,inversion, transformation or any other method of gene or chromosomeengineering to include variations thereof. In addition, starch derivedfrom a plant grown from artificial mutations and variations of the abovegeneric composition, which may be produced by known standard methods ofmutation breeding, are also suitable herein.

Typical sources for the starches are cereals, tubers, roots, legumes andfruits. The native source can be corn, pea, potato, sweet potato,banana, barley, wheat, rice, sago, amaranth, tapioca, arrowroot, canna,sorghum, and waxy or high amylose varieties thereof. As used herein, theterm “waxy” is intended to include a starch containing at least about 95percent by weight amylopectin and the term “high amylose” is intended toinclude a starch containing at least about 40 percent by weight amylose,more particularly at least about 70 percent amylose.

Native starches suitable for the present invention may be modified usingany modification known in the art, including physical, chemical and/orenzymatic modifications, to obtain the desired film attributes.

Physically modified starches, such as sheared starches, orthermally-inhibited starches described in the family of patentsrepresented by WO 95/04082 and resistant starches described in thefamily of patents represented by U.S. Pat. No. 5,593,503, may besuitable for use herein.

Chemically modified products are also intended to be included as thebase material and include, without limitation, those which have beencrosslinked, acetylated and organically esterified, hydroxyethylated andhydroxypropylated, phosphorylated and inorganically esterified,cationic, anionic, nonionic, amphoteric and zwitterionic, and succinateand substituted succinate derivatives thereof. Such modifications areknown in the art, for example in Modified Starches: Properties and Uses,Ed. Wurzburg, CRC Press, Inc., Florida (1986).

Conversion products derived from any of the starches, including fluidityor thin-boiling starches prepared by oxidation, enzyme conversion, acidhydrolysis, heat and or acid dextrinization, thermal and or shearedproducts may also be useful herein.

Further suitable are pregelatinized starches which are known in the artand disclosed for example in U.S. Pat. Nos. 4,465,702, 5,037,929,5,131,953, and 5,149,799. Conventional procedures for pregelatinizingstarch are also known to those skilled in the art and described forexample in Chapter XXII—“Production and Use of Pregelatinized Starch”,Starch: Chemistry and Technology, Vol. III-Industrial Aspects, R. L.Whistler and E. F. Paschall, Editors, Academic Press, New York 1967.

Any starch or starch blend having suitable properties for use herein maybe purified by any method known in the art to remove starch off colorsthat are native to the polysaccharide or created during processing.Suitable purification processes for treating starches are disclosed inthe family of patents represented by EP 554 818 (Kasica, et al.). Alkaliwashing techniques, for starches intended for use in either granular orpregelatinized form, are also useful and described in the family ofpatents represented by U.S. Pat. No. 4,477,480 (Seidel) and U.S. Pat.No. 5,187,272 (Bertalan et al.).

Additional suitable starches are starches capable of emulsifying orencapsulating an active ingredient so that there is no need foradditional encapsulating or emulsifying agents. Such starches include,without limitation, hydroxyalkylated starches such as hydroxypropylatedor hydroxyethylated starches, and succinylated starches such asoctenylsuccinylated or dodecylsuccinylated starches. In one embodiment,emulsifying or encapsulating starches are used so that a solution ordispersion of the film material (starch component, active agent, andoptional additives) may be stored for later processing. Thehydroxyalkylated starches have the added advantage of forming a softerfilm so that there is less or no need for a plasticizer.

To facilitate processing of the films, the starches may be partiallyconverted to reduce the viscosity and allow for the production of a highsolids starch dispersion/solution, such as a 30% solids starchdispersion/solution. Suitable starches in one embodiment are those witha viscosity of at least about 1000 cps at 10% solids and a viscosity ofno more than about 100,000 cps at 30% solids.

In another embodiment, suitable starches have a flow viscosity of atleast about 7 seconds. In another embodiment, suitable starches haveflow viscosity of at least 10 seconds and no more than about 19 seconds.In yet another embodiment, suitable starches have a flow viscosity of nomore than about 15 seconds. Flow viscosity, as used herein, is measuredby the test defined in the Examples section, below.

The molecular weight of the starch is also important to itsfunctionality in a film, particularly to film strength. For example,dextrins alone are not suitable in the present application.

The starch component may be a single modified or native starch, a blendof modified starches, or a blend of modified and native starches. Blendsmay be useful to lower the cost of the film or to more easily achieve avariety of desirable properties and functionalities.

Examples of commercial starches, with their INCI names, that may be usedin the present invention comprise the following: from National Starchand Chemical Company, the AMAZE® polymer (corn starch modified),CELQUAT® LS-50 resin (polyquaternium-4/hydroxypropyl starch copolymer),STRUCTURE® XL polymer (hydroxypropyl starch phosphate), DRY FLO®PClubricant (aluminum starch octenylsucinate), DRY FLO®AF lubricant (cornstarch modified), DRY FLO® ELITE LL lubricant (aluminum starchoctenylsuccinate (and) lauryl lysine), DRY FLO® ELITE BN lubricant (INCIname: aluminum starch octenylsuccinate (and) boron nitride), PURITY®21Cstarch (zea mays (corn) starch), TAPIOCA PURE (tapioca starch),thermally inhibited corn, potato, tapioca, high amylase, and waxy maizestarches sold under the NOVATION trademark, and resistant starches soldunder the HI-MAIZE trademark; from the Croda Company, CROSTYLE MFP(trimethyl quaternized maize starch); from ONDEO Nalco, SENSOMER CI-50(starch hydroxypropyltrimonium chloride).

The natural polymer also may comprise without limitation a cellulosicmaterial such as carboxymethyl cellulose, hydroxypropyl cellulose,microcrystalline cellulose, ethylcellulose, cellulose acetate phthalate,cationic cellulose derivatives such as polyquaternium-4 (CELQUAT L-200and CELQUAT H-100 polymers from National Starch and Chemical Company)and polyquaternium-10 (CELQUAT SC-240C and CELQUAT 230M polymers fromNational Starch and Chemical Company), or a gum, xanthan (such as theAMAZE™XT polymer from National Starch and Chemical Company), pullulan,hydrocolloids, carageenan, alginate, casein, gelatin, and solubilizedproteins.

In films containing both synthetic and natural hair fixative polymers,the ratio of synthetic to natural hair fixative polymer based on theweight of the total fixative polymer is from about 5:95 to about 95:5;in another embodiment from about 20:80 to about 75:25; in anotherembodiment from about 25:75 to about 60:40; in another embodiment fromabout 30:70 to about 55:45; in another embodiment from about 35:65 toabout 42:58; in another embodiment from about 29:71 to about 33:67.

The hair fixative films of the invention contain a hair fixative polymeror blend of different hair fixative polymers. One skilled in the art canadd additional materials to the hair fixative film compositions tomodify the performance or physical properties of the film. For instance,one skilled in the art knows that many synthetic fixative polymers mayrequire the addition of a base and/or plasticizer to make the filmssoluble, less brittle, and/or to optimize on-hair performance.Plasticizing agents are also useful to add to the flexibility of filmscontaining natural or synthetic fixative polymers. The film should bestrong, yet flexible and should not be overly brittle. It must beblocking and moisture resistant so that it does not adhere to itself,yet able to dissolve or disintegrate quickly when exposed to water orother polar solvent such as when wetted in the hand.

Such plasticizing agents are known in the art and include withoutlimitation dimethicone copolyols, polyols, polycarboxylic acids, andpolyesters. Examples of useful dimethicone copolyols include, but arenot limited to PEG-12 Dimethicone, PEG/PPG-18/18 Dimethicone, and PPG-12Dimethicone. Examples of useful polyols include, but are not limited toethylene glycol, propylene glycol, sugar alcohols such as sorbitol,manitol, maltitol, lactitol; mono-di- and oligosaccharides such asfructose, glucose, sucrose, maltose, lactose, and high fructose cornsyrup solids and ascorbic acid. Examples of polycarboxylic acidsinclude, but are not limited to, citric acid, maleic acid, succinicacid, polyacrylic acid, and polymaleic acid. Examples of polyestersinclude, but are not limited to, glycerol triacetate,acetylated-monoglyceride, diethyl phthalate, triethyl citrate, tributylcitrate, acetyl triethyl citrate, acetyl tributyl citrate.

Other examples of plasticizers include, but are not limited to mineraloils, vegetable oils, triglycerides, lanolins and their derivatives,unsaturated fatty acids and their derivatives, silicones, and someemollients; humectants such as glycerol, sorbitol, lactates (includingbut not limited to sodium, ammonium, and potassium salts), polyols (e.g.propylene glycol), polyethylene glycol (200-600), and Sorbeth-30;natural moisturizing factors (NMFs) such as urea, lactic acid, andsodium pyrrolidone carboxylic acid (PCA); liposomes, natural and vegetalmoisturizing agents such as glycerol, serine, chitosan PCA, sodiumhyaluronate, hyaluronic acid, microsponges, soluble collagen, modifiedprotein, monosodium L-glutamate, lecithins and phospholipids and theirderivatives; alpha and beta hydroxy acids such as glycolic acid, lacticacid, citric acid, maleic acid and salicylic acid; polymericplasticizers such as polysaccharides and their derivatives,polyacrylates, and polyquaterniums; proteins and amino acids such asglutamic acid, aspartic acid, and lysine.

The plasticizers will be present in a plasticizing effective amount. Inone embodiment, the plasticizer will be present in the hair fixativefilm in an amount from about 0 to about 30 percent based on the weightof the dry film composition. In yet another embodiment, the plasticizerwill be present in an amount from about 5 to about 15 percent based onthe weight of the dry film composition. In hair fixative films in whichthe natural fixative is at least 60% (wt/wt) based upon the totalfixative, a plasticizer may be present in an amount greater than 15percent based upon the weight of the natural polymer, but not greaterthan about 30 percent based upon the weight of the dry film; in anotherembodiment, greater than 17 percent based upon the total weight of thenatural polymer and less than about 30 percent based upon the weight ofthe total dry film composition; and in yet another embodiment, greaterthan 20 percent based upon the total weight of the natural polymer andless than about 30 percent based upon the weight of the total dry filmcomposition. Some plasticizers may be added to the solution to be driedto make the hair fixative film at a dosage above the desired end dosage,and a portion of the plasticizer, the excess portion, may then be drivenoff with heat during film formation. One skilled in the art would knowhow to adjust the plasticizer to balance film properties.

As known in the art, those hair fixative polymers which contain acidicgroups and are insoluble in water are usually used in their neutralized,water-soluble or water dispersible form.

Suitable neutralizing agents which may be included alone or incombination in the composition of the present invention include, but arenot limited to, alkyl monoamines containing from about 2 to 22 carbonatoms such as triethylamine, stearylamine and laurylamine, and aminoalcohols such as triethanolamine, 2-amino-2-methyl-1,3-propanediol and2-amino-2-methyl-1-propanol, and inorganic neutralizers such as sodiumhydroxide and potassium hydroxide. Other combinations of usefulneutralizing agents are described in U.S. Pat. No. 4,874,604 to Sramek.

With polymers requiring neutralization, the neutralizer will be presentin an amount effective to neutralize a percentage of the polymer's freeacid groups and render the polymer water-soluble or water-dispersible.In one embodiment, the neutralizer will be present in an amountsufficient to neutralize the free acid groups of the fixative polymerfrom about 8 percent to 100 percent neutralization. In anotherembodiment, the free acid groups of the fixative polymer will beneutralized from about 25 percent to 100 percent. In another embodiment,the free acid groups of the fixative polymer will be neutralized fromabout 50 percent to 100 percent. In another embodiment, the free acidgroups of the fixative polymer will be neutralized from about 70 percentto 100 percent. In yet another embodiment, the free acid groups of thefixative polymer will be neutralized from about 80 to 100 percent.

The base may also be used in excess of 100 percent neutralization toincrease the solution pH or to plasticize the resin in addition toneutralization of the polymer acid groups.

The hair fixative film composition may also include other optional filmforming and hair fixative ingredients known in the art. These optionalingredients include, without limitation, thickeners, emulsifiers,aesthetic modifiers, UV filters, humectants (such as hydroxyethyl urea,available from Nationla Starch and Chemical Company under the trademarkHYDROVANCE), lubricants, skin whitening ingredients, silicones, powders,deviscosifying agents, moisturizers, emollients, solvents, chelatingagents, vitamins, antioxidants, botanical extracts, pH adjusting agents,preservatives, fragrances, waterproofing agents, active ingredients(anti-aging agents, firming or toning agents, etc.), dyes, pigments,colors, polymers, conditioning agents, rheology modifiers, surfactants,opacifiers, foaming agents, heat generating agents and/or effervescingagents, glitter and decorative beads and shapes.

The effervescing agents may be one or more materials that effervescewhen coming into contact with water. In one embodiment, the effervescentelement of the film is comprised of two components. Suitable fistcomponents comprise any acids present in dry solid form such as C₂-C₂₀organic mono- and poly-carboxylic acids. In another embodiment, thefirst component may be alpha- and beta-hydroxycarboxylic acids; C₂-C20organosulfur acids such as toluene sulfonic acid; and peroxides such ashydrogen peroxide. In one embodiment hydroxycarboxylic acids compriseadipic, gutaric, succinic, tartaric, malic, maleic, lactic, salicylic aswell as acid forming lactones such as gluconolactone and glucarolactone.In another embodiment, the acid is citric acid. Also suitable as theacid material are water soluble synthetic or natural polymers such aspolyacrylates (e.g., encapsulating polyacrylic acid), cellulosic gums,polyurethane and polyoxyalkalene polymers. The term “acid” is meant toinclude any substance which when dissolved in deionized water at 1%concentration will have a pH of less than 7; in another embodiment lessthan 6.5; in another embodiment less than 5. The acids in one embodimentare in the solid form at 25° C., (i.e., having melting points no lessthan 25° C.). Concentration of the acid should range from about 0.5 toabout 80 percent based on the final weight of the fixative film; inanother embodiment from about 10 to about 65 percent; in anotherembodiment from about 20 to 40 percent.

Suitable second components of the effervescent element comprise alkalinematerials. An alkaline material is a substance which can generate a gassuch as carbon dioxide, nitrogen or oxygen (i.e., effervesce), whencontacted with water and the acidic material of the first component.Suitable alkaline materials comprise anhydrous salts of carbonates andbicarbonates and alkaline peroxides. In one embodiment, the alkalinematerial is sodium or potassium bicarbonate. Amounts of alkalinematerial may range from about 1 to about 40 percent based upon theweight of the fixative film; in another embodiment from about 5 to 35percent; in another embodiment from about 15 to about 30 percent; inanother embodiment from about 25 to about 35 percent.

The acid and alkaline components of the effervescing element may bephysically separated until combined with water. Such methods ofseparation comprise formulating a bi-layer film wherein one layercontains the acid component and the other layer contains the alkalinecomponent. Another method of physical separation comprises encapsulationof at least one component in a third material. Such methods of producingbi-layer films and encapsulation of acid or basic materials are known inthe art.

The heat-generating component of a film may be one material or acombination of more than one material that generates heat when cominginto contact with water. Examples of heat-generating combinationsinclude combinations of acids and bases. In another embodiment, theheat-generating combination is of an oxidizing reagent and a reducingagent. Such oxidizing and reducing agents may be selected broadly fromthe various compounds of this nature available. Examples of oxidizingagents comprise chlorates, perchlorates, permanganates, persulfates,peroxides, nitrates, metal oxides, such as copper oxide, lead oxide, andiron oxide, and perborates. In one embodiment, the oxidizing agent isselected from the group consisting of hydrogen peroxide, urea peroxide,sodium peroxide, sodium perborate, sodium persulfate, ammoniumpersulfate, potassium persulfate, and mixtures of any of two or more ofthe foregoing. Examples of reducing agents comprise magnesium, zinc,aluminum and iron; sulfites, thio-sulfates, thioureas,imidazolinethiones, thiotrazoles, thiopyridines, thio-pyrimidines,thiols, thio-acids, sulfoxides, xanthates, ortho- and para-polyhydroxybenzenes, aldehydes, and glycols.

The oxidizing and reducing agents may be physically separated untilcombined with water. Such methods of separation comprise formulating abi-layer film wherein one layer contains the oxidizing component and theother layer contains the reducing component. Another method of physicalseparation includes encapsulation of at least one component in a thirdmaterial.

Single components that generate heat when combined with water are thosehaving an appreciable heat of solution or dilution in water, e.g. thecombination of water and ethylene glycol and the combination of waterand salts such as aluminum sulfate, calcium chloride, copper sulfate,ferric chloride, magnesium chloride, magnesium sulfate, etc. In oneembodiment, the single heat-generating component may range from about 1to about 40 percent based upon the weight of the fixative film; inanother embodiment from about 5 to 35 percent; in another embodimentfrom about 15 to about 30 percent; in another embodiment from about 25to about 35 percent

The hair fixative films of the present invention are formed bytechniques known in the industry. For example, the hair fixative may bedispersed with the other film components in water or other solvent anddried into film form. In the alternative, the fixative polymer and otherdry components may be blended and then dispersed with any additionalfilm components in water or other solvent and dried into film form.Films may be formed from such dispersions or solutions by shaping itinto a solidified form of a suitable thickness by any technique known inthe art including, but not limited to, wet casting, freeze-drying, andextrusion molding. The dispersion or solution may also be directlycoated or sprayed onto another product and dried to form a film.

In one embodiment, the films of the present invention are processed bypreparing a coating formulation by making a solution or dispersion ofthe film components, applying the mixture to a substrate, using knife,bar or extrusion die coating methods, drying the coated substrate toremove the majority of the solvent, and removing the film from thesubstrate. Suitable substrates include, but are not limited to, siliconeelastomers, metal foils and metalized polyfoils, composite foils orfilms containing polytetrafluoroethylene materials or equivalentsthereof, polyether block amide copolymers, polyurethane, polyvinylidene,polyester, and other such materials useful in the art as releasablesubstrates. The hair fixative film may be dried at standard temperatureand pressure or elevated temperature and/or pressure, or lowertemperature and/or pressure compared to standard conditions.

Dissolution rate is determined by measuring the time it takes a squareinch of film to disintegrate in a beaker of polar solvent. In oneembodiment, the hair fixative film will disintegrate in 25° C. water inless than about 15 minutes. In another embodiment, the hair fixativefilm will disintegrate in 25° C. water in less than 10 minutes. Inanother embodiment, the hair fixative film will disintegrate in 25° C.water in less than 5 minutes. In another embodiment, the hair fixativefilm will disintegrate in 25° C. water in less than 2.5 minutes. Inanother embodiment, the hair fixative film will disintegrate in 25° C.water in less than 1 minutes. In another embodiment, the hair fixativefilm will disintegrate in 25° C. water in less than 45 seconds. Inanother embodiment, the hair fixative film will disintegrate in 25° C.water in less than 30 seconds. In another embodiment, the hair fixativefilm will dissolve in 25° C. ethanol in less than 5 minutes. In anotherembodiment, the hair fixative film will disintegrate in 25° C. ethanolin less than 2.5 minutes. In another embodiment, the hair fixative filmwill disintegrate in 25° C. ethanol in less than 1 minutes. In anotherembodiment, the hair fixative film will disintegrate in 25° C. ethanolin less than 45 seconds. In another embodiment, the hair fixative filmwill disintegrate in 25° C. ethanol in less than 30 seconds.

The films may not be completely dried in that some degree of water orother solvent remains. The amount of solvent present in the film may becontrolled to obtain desired functionality. For example, more solventtypically results in a more flexible film, while too much solvent mayresult in a film that will block and be tacky. Some solvent is generallyin the hair fixative film as used. In one embodiment, the remainingsolvent in the fixative film may be in the range from about 0 to about25 percent, based on the weight of the film; in another embodiment, fromabout 1 to about 20 percent solvent remains; in another embodiment, fromabout 5 to 16 percent solvent remains; in another embodiment, about 10to 15 percent solvent remains.

The film thickness may be in the range of about 1 to 500 microns, and inone embodiment the film has a thickness from about 25 to about 100microns. In another embodiment, the film has a thickness from about 25to 60 microns, and in yet another embodiment the film has a thicknessfrom about 25 to about 50 microns.

The resultant films are lightweight and easy to carry. They aresufficiently strong and apparently flexible so as to be easilydispensable and handled.

The films exhibit moisture and blocking resistance, yet are wetted whenexposed to water or a polar solvent followed by rapid dissolution and/ordisintegration. The wettability and dissolution rates of the hairfixative films may be modified by one skilled in the art to target aspecific delivery profile. For example, more rapid dissolution ofcarboxylated hair fixative polymers may be achieved using neutralizationand/or plasticization. Neutralization of carboxylic groups of hairfixative polymers creates charged groups along the polymer backbonewherever a carboxyl group is neutralized. The charged polar groups makethese sections of the polymer more soluble in polar solvents than ifthese carboxyl groups were not neutralized.

The hair fixative films of the present invention provide excellent highhumidity resistance to the hair style. In one embodiment of theinvention, the fixative film will give an average high humidity curlretention of greater than 15 percent after 2 hrs. In another embodimentthe hair fixative films give a high humidity curl retention greater than20 percent after 2 hrs. In another embodiment, the hair fixative filmsgive a high humidity curl retention greater than 30 percent after 2 hrs.In another embodiment, the hair fixative films give a high humidity curlretention greater than 60 percent after 2 hrs. “High humidity curlretention”, as used herein, is measured by the test defined in theExamples section below. One skilled in the art would know how to selecthair fixative polymers or formulate to provide more or less humidityresistance to a hair fixative film.

The hair fixative films of the present invention also provide stiffnessto the hair. In one embodiment, the hair stiffness is from about 0.004Joules to about 0.030 Joules. In another embodiment, the hair stiffnessis from about 0.008 Joules to about 0.030 Joules. In another embodiment,the hair stiffness is from about 0.012 Joules to about 0.025 Joules. Inanother embodiment, the hair stiffness is from about 0.015 Joules toabout 0.025 Joules. “Stiffness”, as used herein, is measured by thestandard test defined in the Examples section below.

The hair fixative films of the present invention permit the use of highperformance polymers that can not be used together in otherapplications. The formulation of these polymers into a hair fixativefilm gives a novel, fun application and overcomes some of thelimitations associated with other applications. For example, someanionic and cationic polymers may be combined and formed into films inratios that would form an insoluble precipitate in aqueous solutions orhave unacceptable rheology in gel or spray applications. In anotherexample, PVP and sulfonated polystyrene forms a gel that is so viscousat high concentrations that it may not be used in traditional hairfixative spray applications, but this combination may be formed into afilm and used as a hair fixative in the present invention.

A user of the personal care composition may apply the film to the hairin a number of different ways. One method of application compriseswetting the hands, placing the composition in the hands, distributingthe film over the hands and then applying by passing the hands throughthe hair. In an alternate embodiment, the user may place the filmdirectly on wet hair and distribute the film as desired through theirhair. In another embodiment, the film may be placed directly in thehands and then wetted and distributed throughout the hair. Any othersimilar application method may be used.

In another method of application of the hair fixative films of thepresent invention, the hair fixative film may be dissolved or dispersedin another application type to add or increase the hair fixativeproperties of the application. For instance, in one embodiment, the hairfixative film may be added to an existing hair fixative gel to increasethe holding power of the gel. In another embodiment, the hair fixativefilm is added to a non-aerosol hair spray to increase the holding power.In another embodiment, the hair fixative film is added to a curldefining lotion to add hair fixative properties.

In another method of application of the hair fixative films of thepresent invention, the hair fixative film may be applied to the hair byadding another product to a hair fixative film to dissolve or dispersethe hair fixative film and then apply to the hair. For instance, in oneembodiment, a quantity of hair gel may be added to a film in the handand mixed in the hand to dissolve or disperse the film so that it may bethen applied to the hair together. In another embodiment, a hair sprayis sprayed onto the film in the hand then mixed by rubbing with thehands and applied to the hair together. In another embodiment, aquantity of a hair product containing a polar solvent such as a lotion,mousse, hair wax, pomade, or shine product may be added to the film todisperse or dissolve the film and then applied to the hair together.

EXAMPLES

The following examples are presented to further illustrate and explainthe present invention and should not be taken as limiting in any regard.

All percents used are on a weight/weight basis. In the examples below,the following materials in Table 1 are used:

TABLE 1 Tradename Chemical or CTFA Name Function AMP 95 AminomethylPropanol Neutralizer (95% in water) CELQUAT ®Polyquaternium-4/Hydroxypropyl Fixative LS-50 resin Starch CopolymerAMAZE ® polymer Corn starch Modified Fixative PVP K-90Polyvinylpyrrolidone Fixative AMPHOMER ® Octylacrylamide/acrylates/Fixative polymer butylaminoethyl methacrylate copolymer RESYN ® 28-2930VA/Crotonates/Vinyl Neodecanoate Fixative polymer Copolymer DynamX ™Polyurethane-14 (and) Fixative polymer AMP-Acrylates Copolymer LUVISETPUR Polyurethane-1 Fixative LUVITEC 64 PVP/VA Fixative Pulver LUVISKOL73W PVP/VA Fixative Propylene Glycol Plasticizer Dow Corning 193 PEG-12Dimethicone Plasticizer Surfactant Dipropylene Glycol PlasticizerCROPEPTIDE W Hydrolyzed Wheat Protein Plasticizer GLYDANT Plus DMDMHydantoin (and) Preservative lodopropynyl Butylcarbamate

In the examples below, the starches used are as follows:

-   -   Acetylated=acetylated (5% treatment) high amylose (70%) corn        starch commercially available from National Starch and Chemical        Company (Bridgewater, N.J., USA).    -   Converted=mannox converted waxy corn starch commercially        available from National Starch and Chemical Company        (Bridgewater, N.J., USA).    -   Corn=native corn starch commercially available from National        Starch and Chemical Company (Bridgewater, N.J., USA).    -   OSA waxy 1=mannox degraded octenylsuccinated waxy corn starch        commercially available from National Starch and Chemical Company        (Bridgewater, N.J., USA).    -   PO waxy 1=Hydroxypropylated (8.5% treatment) waxy corn starch        with a water fluidity of 35* commercially available from        National Starch and Chemical Company (Bridgewater, N.J., USA).    -   PO waxy 2=Agglomerated hydroxypropylated (8.5% treatment) waxy        corn starch with a water fluidity of 35* commercially available        from National Starch and Chemical Company (Bridgewater, N.J.,        USA).    -   PO waxy 3—Hydroxypropylated (8.5% treatment) waxy corn starch        with a water fluidity of 15* commercially available from        National Starch and Chemical Company (Bridgewater, N.J., USA).    -   Pullulan=pullulan (grade PF-20, molecular weight of 200,000)        commercially available from Hayishibara Co., Ltd. (Japan).    -   Tapioca=native tapioca starch, commercially available from        National Starch and Chemical Company (Bridgewater, N.J., USA).

Example 1 Procedures

In the examples below, the procedures used are as follows:

Film Casting: films were cast by drawing down the solution/dispersionusing a Braive Laboratory Bar Coater, either dried at room temperatureovernight or dried in an oven at 250° F. (121° C.).

Blocking resistance: films are stacked on top of each other, conditionedfor 24 hours at 104° F. (40° C.) and 75% relative humidity, then pulledapart to see whether or not they block (adhere).

Dissolution time: dissolution time is determined by measuring the time,in seconds, that it takes for a square inch (6.45 cm²) of film todisintegrate in a beaker of polar solvent at 25° C.

Flow Viscosity: flow viscosity is measured as follows. The starch isslurried in water and jet cooked at 149° C. until fully gelatinized. Thesolids are adjusted to 5% (w/w). the temperature of the starch solutionis controlled at 22° C. A total of 100 ml of the starch dispersion ismeasured into a graduated cylinder. It is then poured into a calibratedfunnel while using a finger to close the orifice. A small amount isallowed to flow into the graduated to remove any trapped air, and thebalance is poured back into the funnel. The graduated cylinder is theninverted over the funnel so that the contents draw (flow) into thefunnel while the sample is running. Using a timer, the time required forthe 100 ml sample to flow through the apex of the funnel is recorded.

The glass portion of the funnel is a standard 58°, thick-wall,resistance glass funnel whose top diameter is about 9 to 10 cm with theinside diameter of the stem being approximate length of 2.86 cm form theapex, carefully firepolished, and refitted with a long stainless steeltip which is 5.08 cm long with an outside diameter of 0.9525 cm. Theinterior diameter of the steel tip is 0.5951 cm at the upper end whereit is attached to the glass stem; it is 0.4445 cm at the outflow end,with the restriction in the width occurring at about 2.54 cm from theends. The steel tip is attached to the glass funnel by means of a Teflontube. The funnel is calibrated so as to allow 100 ml of water to gothrough in 6 seconds using the above procedure.

Stiffness: “stiffness” is the amount of work required to deflect a hairswatch 10 mm at a rate of 50 mm/min. Stiffness is measure using thefollowing procedure. Five 6 inch (15.24 cm) virgin brown hair swatchesare used for each sample to be tested. Polymer solids are set at 0.75percent for each formulation and 2 grams of aqueous polymer solution isapplied to each hair swatch. Each swatch is tared and then dipped intothe aqueous polymer solution so that it is wetted thouroughly. Theswatches are then drawn between the thumb and forefinger and blottedwith a paper towel until the weight of each swatch is 2.0 grams plus orminus 0.1 grams more than the tare weight. The excess weight is theweight of the solution applied to the swatch and equates to 0.015 gramsof polymer applied to the hair swatch. After the solution is applied,the swatches are allowed to air dry in a constant temperature andhumidity room, maintained at 72° F. (22.2° C.) and 50 percent relativehumidity, prior to testing.

The swatches are tested the next day using a Diastron MTT 160 miniaturetensile tester with a stiffness testing jig available from themanufacturer of the instrument. Each hair swatch is then laid across twolower horizontal prongs (or bars) separated by 10 cm and runningperpendicular to direction the hair is laid to be evaluated one swatchat a time. The Diastron instrument then applies a measured force, inNewtons, with a 1 cm diameter horizontal bar perpendicular to thehorizontal swatch and between the two lower bars to bend the swatch adistance of 10 mm. The work, in Joules, is the stiffness of the hairswatch with a certain composition applied to the hair swatch. Thestiffness for the five 6 inch (15.24 cm) swatches are then recorded andanalyzed statistically to determine an average stiffness for the sampletested.

High Humidity Curl Retention: it is known in the art that high humiditycurl retention is a measurement of how well a fixative formulation willmaintain hair in a given style in high humidity conditions and is astandard and important test of a hair fixatives performance. The curlretention properties of hair fixative films of the present invention aremeasured using this procedure and compared to each other. The test isconducted at 72° F. (22° C.) and 90 percent Relative Humidity over aperiod of 2 hours. The procedure allows for statistical analysis offormulation variables. The percentage curl retention is calculated bythe following formula: Curl Retention %=100×(L−L_(t))/(L−L₀), whereL=length of hair fully extended, L₀=initial curl length, L_(t)=curllength at a given time t.

The test is performed on 10 inch (25.4 cm) long×2 gram tresses ofEuropean virgin brown hair (9 replicate tresses per sample). Cleaned wethair tresses are combed through to remove tangles and excess water isremoved. Two grams of 0.75 percent hair fixative film solution isapplied to each tress, gently “worked into” the hair tress and combedthrough. Curls of hair are made using a ½ inch (1.27 cm) diameter Teflonmandrel, placed on a tray and dried in an oven overnight. The curls aresuspended from the bound end of the tress on graduated transparent curlretention boards. An initial curl length reading is taken before placingboards and curls into the constant temperature and humidity chamber forexposure. Then curl lengths are recorded at 15 minutes, 30 minutes, 60minutes, 90 minutes and 2 hours. Curl retention averages are thencalculated. The curl retention results after 2 hours are tabulated inTable 6. The results demonstrate that all the hair fixative filmcompositions provide some curl retention properties; however, the highperformance polymers provide dramatically better humidity resistance.One skilled in the art would be able modify the High Humidity CurlRetention performance of a film by choice of polymer type and amountchoice of plasticizer type and amount included in the formulation.

Example 2 Comparison of Various Starch Films

Films were made of a variety of starches and pullulan and the films weretested subjectively for flexibility, clarity, tack, blocking resistanceand objectively for dissolution time. The results are shown in Table 2below.

TABLE 2 Flow Vis- Starch/ Apparent Block- Dissolution cosity Pullulanflexibility Clarity Tack ing Time (sec) (sec) Pullulan Flexible ClearNone None 9 — Po waxy 1 Flexible Clear None None 6.5 12.1 Corn FlexibleHazy None None >120 17.2 Tapioca Flexible Clear None None 83 35.0Acetylated Flexible Hazy None None >120 11.9 PO waxy 3 Flexible ClearNone None 36 19.6 OSA waxy 1 Flexible Clear None None 42 10.1 ConvertedFlexible Clear None None 8.5 10.1 PO waxy Flexible Clear None None 13.5— 2:Pullulan 90:10 PO waxy Flexible Hazy None None 7.5 — 2:Corn 90:10

Example 3 Hair Fixative Film Ingredient Compatibility, PlasticizerLevels, and Use as Hair Fixatives

Tables 3, 4 and 5, below, contain representative formulations embodyingthe present invention where the ingredients are combined and/or mixed toform a liquid product composition which then may be dried at ambienttemperature and pressure, at elevated or lower temperature, and/or atelevated or lower pressure to form the hair fixative film.

TABLE 3 Formula # and Weight (grams) Ingredients 1 2 3 4 5 6 AMP 95 — —6.4 0.9 4.6 — CELQUAT LS-50 21.3 — — — — — resin AMAZE polymer — 15.5 —23.6 — 23.8 PVP K-90 — 7.5 — 5.1 — — AMPHOMER — — 37.4 5.1 — — polymerDynamX polymer — — — — — 83.8 Luvitec 64 Pulver — — — — — — RESYN28-2930 — — — — 50.0 — polymer Propylene Glycol 1.3 — 4.3 6.2 5.6 2.5DOW CORNING 2.5 — 1.1 — — — 193 Surfactant Dipropylene Glycol — 1.3 — —— — CROPEPTIDE W — 0.8 — 1.2 — — Water 225 225 201 183.0 189.9 140

TABLE 4 Formula # and Weight (grams) Ingredients 7 8 9 10 11 12 CELQUATLS-50 21.0 — — — — — resin LUVITEC 64 9.7 — — — — — pulver AMPHOMER —3.8 37.4 — — 3.4 polymer AMAZE polymer — 22.9 — — — 21.5 PVP K-90 — 11.5— — 47.5 10.2 BALANCE CR — — — 100.0 — — polymer AMP 95 9.7 0.7 6.3 6.1— 0.6 Propylene glycol 2.5 4.4 6.6 5.0 — 11.9 Dipropylene glycol — — — —5.3 — CROPEPTIDE W — 1.3 — — — — Water 216.8 180.5 199.7 138.9 197.2202.4

TABLE 5 Formula # and Weight (grams) Ingredients 13 14 15 16 17 CELQUATLS-50 — 21.0 21.0 — — resin LUVITEC 64 — 9.7 9.7 — — Pulver AMPHOMER 3.4— — 3.4 3.4 polymer AMAZE polymer 21.4 — — 21.5 21.5 PVP K-90 10.1 — —10.2 10.2 AMP 95 0.6 — — 0.6 0.6 Propylene glycol 15.2 10.3 13.2 3.9 6.2Water 199.1 209.0 206.0 210.7 208.2

Formulation 1-17's ingredients were combined and formed acceptable filmsafter drying.

Formulation 1 demonstrates the ability to formulate starch and cationiccellulose together where the polymers would separate over time if keptin solution and demonstrates the use of dimethicone copolyol andpropylene glycol as plasticizer.

Formulation 2 demonstrates the ability to formulate nonionic modifiedstarch and nonionic synthetic into an acceptable film and demonstratesthe use of the plasticizers dipropylene glycol and CROPEPTIDE W.

Formulation 3 demonstrates the use of an amphoteric synthetic polymerand neutralization in combination with plasticizers to improve filmaesthetics.

Formulation 4 demonstrates the combination of an amphoteric syntheticpolymer in combination with a nonionic starch and synthetic polymer.

Formulation 5 demonstrates the use of an anionic synthetic polymerneutralized with AMP and plasticized.

Formulation 6 demonstrates the use of a nonionic modified starch incombination with a polyurethane and a neutralized acrylate polymer andplasticizer.

Formulation 7 demonstrates the combination of cationic cellulose,modified starch, and an nonionic synthetic copolymer and plasticizerwhere a solution would separate.

Formulation 8 demonstrates the combination of a synthetic amphotericpolymer, a nonionic modified starch, and a nonionic synthetic polymerwith a base and a plasticizer.

Formulation 9 demonstrates a neutralized synthetic amphoteric polymerused as the sole polymer to form an acceptable hair fixative film.

Formulation 10 demonstrates the use of a neutralized anionic syntheticacrylate polymer as the sole polymer to form an acceptable hair fixativefilm.

Formulation 11 demonstrates the use of a nonionic synthetic polymer asthe sole polymer to form a hair fixative film.

Formulation 12 demonstrates the combination of a neutralized amphotericpolymer, a nonionic modified starch, a nonionic synthetic polymer andpropylene glycol as plasticizer at the given level.

Formulation 13 demonstrates the combination of a neutralized amphotericpolymer, a nonionic modified starch, a nonionic synthetic polymer, andpropylene glycol plasticizer at the given level.

Formulation 14 demonstrates the combination of a nonionic modifiedstarch, a nonionic synthetic copolymer, a cationic cellulose withpropylene glycol as plasticizer at the given level.

Formulation 15 demonstrates the combination of a nonionic modifiedstarch, a cationic cellulose, a nonionic synthetic copolymer andpropylene glycol as plasticizer at the given level.

Formulations 16 and 17 demonstrate the formulation of an amphotericsynthetic polymer neutralized with AMP-95, a nonionic synthetic polymer,a natural polymer and two different levels of propylene glycol asplasticizer.

The films from formulas 1 to 17 were then evaluated on hair swatches forhair fixing properties. All formulations were found to have excellenthair fixative properties such as good hold, stiffness, dry combproperties, webbing, spring, and feel and were acceptable as stylingproducts.

Example 4 Hair Swatch Stiffness

The following formulations in Table 6 were evaluated for film stiffnessusing the procedure described above in Example 1. The stiffness valuefor each formulation is reported below the formulation ingredientdosages.

TABLE 6 Formula # and Weight (grams) Ingredients 1 2 3 4* 5* 6* 7 RESYN28-2930 — 1.88 — — — — — polymer LUVISKOL 73W — — — 3.67 — — — AMPHOMER1.87 — — — — — — polymer AMAZE polymer — — — — — — 1.87 PVP K-90 — —1.88 — — — — BALANCE CR — — — — 4.17 — — polymer LUVISET PUR — — — — —6.23 — AMP 95 0.32 0.19 — — 0.25 — — Propylene glycol 0.33 0.10 0.100.33 0.10 0.21 0.21 GLYDANT Plus 1.25 1.25 1.25 1.25 1.25 1.25 1.25Water 246.2 246.6 246.8 244.7 244.2 242.3 246.7 Formulation .008 .004.012 .004 .008 .007 .015 Stiffness (Joules) *Polymer amounts adjustedfor the percent solids of the product as supplied. Formulations 1–7 inTable 6 demonstrate that a formulation may be modified to providedifferent stiffness. These test results correspond directly with thestiff feel of the formulation on the hair when evaluated by human touch.

Example 4 Performance of Hair Fixative Films in High Humidity CurlRetention

The following formulations were prepared and tested for performance inHigh Humidity Curl Retention (HHCR) using the procedure described abovein Example 1 and made into successful films. The formulations tested forHHCR are tabulated in Table 7 below, and the average High Humidity CurlRetention test results for each formula is noted at the end of the tablebelow the ingredient dosages for each formulation.

TABLE 7 Formula # and Weight (grams) Ingredients 1 2 3 4* 5* 6* 7 RESYN28-2930 — 1.88 — — — — — polymer LUVISKIL 73W — — — 3.67 — — — AMPHOMER1.87 — — — — — — polymer AMAZE polymer — — — — — — 1.87 PVP K-90 — —1.88 — — — — BALANCE CR — — — — 4.17 — — polymer LUVISET PUR — — — — —6.23 — AMP 95 0.32 0.19 — — 0.25 — — Propylene glycol 0.33 0.10 0.100.33 0.10 0.21 0.21 GLYDANT Plus 1.25 1.25 1.25 1.25 1.25 1.25 1.25Water 246.2 246.6 246.8 244.7 244.2 242.3 246.7 Average HHCR(%) 46.1424.16 18.27 16.93 39.41 43.68 71.07 Formulations 1–7 in Table 7demonstrate the differences in High Humidity Curl Retention that may beachieved through formulation of a successful hair fixative film.

1. A hair fixative film comprising: (a) at least one hair fixativepolymer comprising a mixture of synthetic and natural polymers, whereinthe ratio of synthetic to natural polymer is from about 20:80 to about75:25 and wherein the synthetic polymers are selected from the groupconsisting of acrylates copolymer, polyurethane, polystyrenic, polyvinylamide, polyvinyl ester, acrylates/octylacrylamide copolymer and mixturesthereof; and (b) a plasticizer; wherein the hair fixative film is anunsupported film and has a thickness of about 1 to about 500 microns,wherein the hair fixative film provides hair stiffness of from about0.004 Joules to about 0.030 Joules when applied to hair, wherein thehair fixative film dissolves when exposed to water, and wherein the hairfixative film has a high humidity curl retention of greater than 30percent after 2 hours.
 2. The film of claim 1, wherein said plasticizeris selected from the group consisting of polyol, polycarboxylic acid,dimethicone copolyol, polyester and mixtures thereof.
 3. The film ofclaim 1, wherein said plasticizer is selected from the group consistingof propylene glycol, glycerol, dipropylene glycol, hydrolyzed wheatprotein, hydrolyzed wheat starch, PEG-12 dimethicone and mixturesthereof.
 4. The film of claim 1 wherein the synthetic polymer isselected from the group of octylacrylamide/acrylates/butylaminoethylmethacrylate, VA/crotonates/vinylneodecanoate copolymer, polyvinylpyrrolidone, polyvinylpyrrolidone/vinylacetate copolymer and mixturesthereof, and the natural polymer is selected from the group consistingof xanthan gum, physically modified starch, chemically modified starch,polyquaternium-10, polyquaternium-4 and mixtures thereof.
 5. The hairfixative film of claim 1 further comprising about 1 to 30 percent of abase based on total weight of the film.
 6. The film of claim 5, whereinthe fixative polymer is a mixture ofoctylacrylamide/acrylates/butylaminoethyl methacrylate, polyvinylpyrrolidone, and modified corn starch, and wherein the ratio ofsynthetic polymer to natural polymer is in a range from about 35:65 toabout 42:58, and wherein the plasticizer is propylene glycol in a rangefrom about 8 to about 11 percent.
 7. The film of claim 5, wherein thefixative polymer is a mixture of polyquaternium-4, corn starch modified,and polyvinylpyrrolidone/vinylacetate copolymer, and wherein the ratioof synthetic polymer to natural polymer is in a range from about 29:71to about 33:67, and wherein the plasticizer is propylene glycol in anamount from about 6 to 9 percent.
 8. A method of styling hair,comprising: dissolving the hair fixative film of claim 1 in a solvent,and applying the hair fixative film to hair.
 9. The film of claim 1wherein the plasticizer is present in an amount of 5 to 30 percent byweight, based on total weight of the hair fixative film.
 10. The film ofclaim 1 wherein the plasticizer is present in an amount of 5 to 15percent by weight, based on total weight of the hair fixative film. 11.The film of claim 1 wherein when the at least one hair fixative polymercomprises at least 60% (wt/wt) of natural polymer based upon totalweight of the hair fixative polymer, the plasticizer is present in anamount greater than 15 percent based upon weight of the natural polymer.12. The film of claim 1 wherein the hair fixative film provides hairstiffness of from about 0.012 Joules to about 0.025 Joules when appliedto hair.
 13. The film of claim 1 further comprising at least oneeffervescing agent.
 14. The film of claim 13 wherein the effervescingagent comprises an acid component and an alkaline component.